Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
  • C07D285/01—Five-membered rings
  • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
  • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
  • C07D285/08—1,2,4-Thiadiazoles; Hydrogenated 1,2,4-thiadiazoles
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
  • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
  • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

• the invention relates to novel alkylsulphinyl- and alkylsulphonyl-1,2,4-thiadiazolyloxyacetamides, to processes and novel intermediates for their preparation and to their use as herbicides.
• alkylsulphinyl- and alkylsulphonyl-1,2,4-thiadiazolyloxyacetamides exhibit herbicidal properties (cf., for example, EP-A 348 737 and the preceding, but not prepublished, Patent Application German Patent Specification 4 317 323 of 25.5.1993).
• the activity of these previously disclosed compounds is not completely satisfactory in all areas of application, particularly at low application rates and concentrations.
• R 1 represents hydrogen or represents alkyl, alkenyl, alkinyl or aralkyl which are in each case optionally substituted
• R 2 represents alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, aralkyl, aryl, alkoxy, alkenyloxy or alkinyloxy which are in each case optionally substituted, or
• R 1 and R 2 together with the nitrogen atom to which they are bonded, form an optionally substituted, saturated or unsaturated nitrogen heterocycle which can contain additional heteroatoms and to which a benzo grouping can be fused, and
• R 3 represents alkyl, aryl or arylalkyl which are in each case optionally substituted
• n and R 3 have the abovementioned meaning
• novel alkylsulphinyl- and alkylsulphonyl-1,2,4-thiadiazolyloxyacetamides of the general formula (I) possess interesting herbicidal properties.
• novel compounds of the formula (I) surprisngly exhibit a substantially more powerful effect against weeds which are difficult to control than does the chemically similar, known compound N-isopropyl- ⁇ -(3-methylsulphinyl-1,2,4-thiadiazol-5-yl-oxy)-acetanilide.
• the invention preferably relates to compounds of the formula (I) in which
• n the numbers 1 or 2
• R 1 represents hydrogen or C 1 -C 8 -alkyl (which is optionally substituted by fluorine, chlorine, cyano or C 1 -C 4 -alkoxy), represents C 2 -C 8 -alkenyl (which is optionally substituted by fluorine and/or chlorine), represents C 2 -C 8 -alkinyl or represents benzyl,
• R 2 represents C 1 -C 8 -alkyl (which is optionally substituted by fluorine, chlorine, cyano or C 1 -C 4 -alkoxy), or C 2 -C 8 -alkenyl (which is optionally substituted by fluorine and/or chlorine), represents C 2 -C 8 -alkinyl, represents C 3 -C 6 -cycloalkyl (which is optionally substituted by chlorine and/or C 1 -C 3 -alkyl), represents C 5 -or C 6 -cycloalkenyl, represents benzyl (which is optionally substituted by fluorine, chlorine and/or C 1 -C 4 -alkyl), represents phenyl (which is optionally substituted by fluorine, chlorine, bromine, iodine, cyano, nitro, C 1 -C 4 -alkyl, trifluoromethyl, C 1 -C 4 -alkoxy and/or C 1 -C 4 -alkylthi
• R 1 and R 2 together with the nitrogen atom to which they are bonded, form a saturated or unsaturated, five- to seven-membered nitrogen heterocycle which is optionally substituted once to three times by C 1 -C 3 -alkyl and which is optionally benzo fused, and
• R 3 represents C 1 -C 8 -alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C 1 -C 4 -alkoxy, dioxolanyl or dioxanyl) or represents phenyl or phenyl-C 1 -C 2 -alkyl (which are in each case optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy),
• the invention relates, in particular, to compounds of the formula (I) in which
• n the numbers 1 or 2
• R 1 represents methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, or n-, i- or s-pentyl (which are in each case optionally substituted by fluorine, chlorine, cyano, methoxy or ethoxy), or represents propenyl, butenyl, propinyl or butinyl,
• R 2 represents methyl, ethyl, n- or i-propyl, n-, i or s-butyl, n-, i- or s-pentyl, or n-, i- or s-hexyl (which are in each case optionally substituted by fluorine, chlorine, cyano, methoxy or ethoxy), represents propenyl, butenyl, pentenyl, propinyl, butinyl or pentinyl, represents cyclopentyl or cyclohexyl (which are in each case optionally substituted by methyl and/or ethyl), represents cyclohexenyl, represents benzyl (which is optionally substituted by fluorine, chlorine and/or methyl) or represents phenyl (which is in each case optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, methoxy or
• R 1 and R 2 together with the nitrogen atom to which they are bonded, represent piperidinyl which is optionally substituted one to three times by methyl and/or ethyl, represent pyrrolidinyl which is optionally substituted once or twice by methyl and/or ethyl, represent perhydroazepinyl or represent 1,2,3,4-tetrahydro(iso)-quinolinyl, and
• R 3 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl (which are in each case optionally substituted by fluorine, chlorine, cyano, methoxy or ethoxy) or represents phenyl or benzyl (which are in each case optionally substituted by fluorine, chlorine, cyano, methyl or methoxy),
• n and R 3 preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I), as being preferred or as being particularly preferred for n and R 3 .
• an oxidizing agent for example hydrogen peroxide
• a reaction auxiliary for example sodium tungstate or sulphuric acid
• a diluent for example water, methanol, formic acid and/or acetic acid
• the precursors of the formula (V) are known and/or may be prepared by processes which are known per se (cf. Chem. Ber. 90 (1957), 892-901; loc. cit. 97 (1964), 225-237; East German Patent Specification 221060; preparation examples)
• hydroxyacetamides which are additionally to be used as starting compounds in the novel process (a) for preparing compounds of the formula (I) are defined generally by the formula (III).
• R 1 and R 2 preferably or in particular have those meanings which have already been indicated above, in connection with the description of the novel compounds of the formula (I), as being preferably or particularly preferred for R 1 and R 2 .
• hydroxyacetamides of the formula (III) are known and/or may be prepared by processes which are known per se (cf. U.S. Pat. No. 4509971 and U.S. Pat. No. 4645525; and, in addition, U.S. Pat. No. 4334073, DE-OS (German Published Specification) 3038598, DE-OS (German Published Specification) 3038636, EP-A 37526, EP-A 348737 and DE-OS (German Published Specification) 3819477.
• alkyl(aryl-, aralkyl-)thio-1,2,4-thiadiazolyloxyacetamides to be used as starting compounds in the novel process (b) for preparing the compounds of the general formula (I) are defined generally by the formula (IV).
• R 1 , R 2 and R 3 preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I), as being preferred or as being particularly preferred for R 1 , R 2 and R 3 .
• the starting compounds of the formula (IV) are known and/or may be prepared by processes which are known per se (cf. EP-A 018497 and EP-A 029171).
• the novel process (a) for preparing the novel alkylsulphinyl- and alkylsulphonyl-1,2,4-thiadiazolyloxyacetamides of the formula (I) is preferably carried out using diluents.
• diluents preferably include hydrocarbons, for example toluene, xylene or cyclohexane, halogeno hydrocarbons, for example methylene chloride, ethylene chloride, chloroform or chlorobenzene, ethers, for example diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, glycol dimethyl ether, tetrahydrofuran and dioxane, alcohols, for example methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol or tert-butanol, ketones, for example
• the salts which are used are preferably chlorides or sulphates of alkali metals or alkaline earth metals, for example sodium chloride, potassium chloride or calcium chloride.
• Sodium chloride is particularly preferred.
• the novel process (a) is advantageously carried out using acid-binding agents.
• Those which are preferably used are strongly basic alkali metal and alkaline earth metal compounds, for example oxides, for example sodium, potassium, magnesium and calcium oxide, hydroxides, for example sodium, potassium, magnesium and calcium hydroxide, alkoxides, for example sodium and potassium tert-butoxide, and/or carbonates, for example sodium, potassium, magnesium and calcium carbonate.
• phase transfer catalyst from 0.01 to 10% by weight (based on the glycolamide of the formula (III) which is employed) of a phase transfer catalyst may be found to be advantageous in some cases.
• a phase transfer catalyst which may be mentioned are:
• Tetrabutylammonium chloride Tetrabutylammonium chloride, tetrabutylammonium bromide, tributyl-methylphosphonium bromide, trimethyl-C 13 /C 5 -alkyl-ammonium chloride, dibenzyl-dimethylammonium methylsulphate, dimethyl-C 12 /C 14 -alkyl-benzylammonium chloride, tetrabutylammonium hydroxide, 18-crown-6, triethylbenzylammonium chloride, trimethylbenzylammonium chloride and tetraethylammonium bromide.
• the reaction temperatures may be varied over a relatively wide range.
• the process is carried out at temperatures of between -50° C. and +110° C., preferably at temperatures of between -20° C. and +80° C.
• novel process (a) is carried out under standard pressure; however, it can also be carried out under elevated or reduced pressure, between approximately 0.1 and 10 bar.
• the novel process (b) for preparing the compounds of the formula (I) is carried out using an oxidizing agent.
• oxidizing agent suitable for oxidizing organic sulphides (thioethers) to corresponding sulphoxides or sulphones are suitable for use in this context.
• suitable oxidizing agents which may be mentioned are: hydrogen peroxide (H 2 O 2 ), performic acid, peracetic acid, perpropionic acid, perbenzoic acid and 3-chloro-perbenzoic acid, and chlorine or hypochlorous acid and its alkali metal or alkaline earth metal salts.
• the novel process (b) is optionally carried out in the presence of a catalyst.
• Salts of metals of the IVth, Vth and VIth subgroup of the periodic system of the elements are preferably used as catalysts in this context. Examples of these catalysts which may be mentioned are sodium (meta)vanadate, sodium molybdate and sodium tungstate.
• the novel process (b) is preferably carried out using a diluent.
• the organic solvents which are customary for oxidation reactions are, together with water, suitable for use as diluents in this context.
• These solvents preferably include chlorinated hydrocarbons, such as methylene chloride, ethylene chloride, chloroform, tetrachloromethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and sec-butanol, and carboxylic acids, such as formic acid, acetic acid and propionic acid.
• chlorinated hydrocarbons such as methylene chloride, ethylene chloride, chloroform, tetrachloromethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene
• reaction temperatures may be varied over a relatively wide range.
• the process is carried out at temperatures of between -20° C. and +60° C., preferably at temperatures of between 0° C. and 40° C.
• novel process (b) is carried out under standard pressure. However, it is also possible to carry it out under elevated or reduced pressure--in general between 0.1 bar and 10 bar.
• the starting compound of the formula (II) and, where appropriate a catalyst are initially introduced into a diluent, and the oxidizing agent is slowly metered in while stirring.
• the reaction mixture is stirred until the reaction is complete and is then worked up in a customary manner (cf. the preparation examples).
• novel active compounds can be used as defoliants, desiccants, haulm killers and, especially, as weedkillers.
• weeds in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the novel compounds act as total or selective herbicides depends essentially on the amount used.
• novel active compounds can be used, for example, in connection with the following plants:
• Monocotyledon crops of the genera Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
• novel active compounds is in no way restricted to these genera, but also extends in the same manner to other plants.
• the compounds are suitable for total weed control, for example on industrial terrain and rail tracks and on paths and areas with or without tree stands.
• the compounds can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pastures, and for selective weed control in annual crops.
• novel compounds of the formula (I) are suitable, in particular, for selectively controlling monocotyledenous and dicotyledonous weeds in dicotyledonous cultures, especially in the pre-emergence process.
• the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and microencapsulations in polymeric substances.
• formulations are produced in a known manner, for example by mixing the novel active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsifiers and/or dispersants and/or foam-formers.
• organic solvents can, for example, also be used as auxiliary solvents.
• Liquid solvents which are mainly suitable are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulphoxide, and water.
• Suitable solid carriers are:
• suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks;
• suitable emulsifiers and/or foam-formers are: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolyzates;
• suitable diss such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolyz
• Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Further additives can be mineral and vegetable oils.
• colourants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian blue, and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
• organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs
• trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
• the formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
• novel active compounds for controlling weeds, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
• Suitable herbicides for the mixtures are known herbicides, for example anilides such as, for example, diflufenican and propanil; arylcarboxylic acids such as, for example, dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids such as, for example, 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters such as, for example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones such as, for example, chloridazon and norflurazon; carbamates such as, for example, chlorpropham, desmedipham, phenmedipham and propham; chloroacetanilides such as, for example, alachlor, acetoch
• a mixture with other known novel active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and soil conditioners, is also possible.
• the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or spreading.
• novel active compounds can be applied both before and after emergence of the plants. They can also be incorporated into the soil before sowing.
• the amount of active compound used can vary within a relatively wide range. It depends essentially on the nature of the desired effect. In general, the rates of application are between 10 g and 10 kg of active compound per hectare of soil surface, preferably between 50 g and 5 kg per ha.
• Example 1 ##STR113## 3.6 g (15 mmol) of 3,5-bis-methylsulphonyl-1,2,4-thiadiazole are dissolved, together with 2.6 g (15 mmol) of hydroxyaceto-2-ethyl-piperidide, in 40 ml of acetone. A solution of 0.6 g of sodium hydroxide in 3.3 ml of water is added dropwise to this at -20° C. The reaction mixture is stirred at -15° C. for 12 hours. It is then diluted to twice its volume with water and the whole is shaken with chloroform. The organic phase is separated off, dried with sodium sulphate and filtered. The solvent is carefully distilled off from the filtrate under a water pump vacuum.
• Example 2 ##STR114## 29.5 g (0.10 mol) of ⁇ -(3-methylthio-1,2,4-thiadiazol-5-yl-oxy)-aceto-N-methyl-anilide are dissolved in 50 ml of methylene chloride. After 100 ml of water has been added, 17.75 g (0.25 mol) of chlorine are passed in, while stirring, within the space of approximately 3 hours. The organic phase is then separated off, washed with water, dried with sodium sulphate and filtered. The solvent is distilled off from the filtrate under a water pump vacuum and the residue is stirred up with a little methanol; the crystalline product is isolated by filtering it off with suction.
• the compound of the formula (I) which are listed in the following Table 2 may also, for example, be prepared in analogy with Preparation Examples 1 and 2 and in accordance with the general description of the novel preparation processes.
• Example (II-1) ##STR470## 148 g (0.73 mol) of 5-chloro-3-methylthio-1,2,4-thiadiazole are dissolved in a mixture comprising 500 ml of methanol and 23 g of concentrated sulphuric acid, and the whole is heated to reflux. 90.6 g (0.8 mol of H 2 O 2 ) of a 30% aqueous solution of hydrogen peroxide are then added dropwise. The reaction mixture is heated under reflux for 3 hours. It is then concentrated and the residue is shaken with chloroform/water; the organic phase is washed with sodium hydrogen carbonate solution and then with water, dried with sodium sulphate and filtered. The solvent is carefully distilled off from the filtrate under a water pump vacuum.
• Example (II-2) ##STR471## 105 g (0.5 mol) of 2,5-bis-ethylthio-1,2,4-thiadiazole and 3.5 g of sodium tungstate are initially introduced into 260 ml of acetic acid, and 475 ml (5.5 mol of H 2 O 2 ) of a 30% aqueous solution of hydrogen peroxide are added dropwise at 20° C. to 30° C. and within the space of approx. 90 minutes. The reaction mixture is stirred at 20° C. for 5 hours and then slowly diluted with 2.5 litres of water. The product, which has resulted in crystalline form during this procedure, is isolated by filtering it off with suction.
• Emulsifier 1 part by weight of alkylaryl polyglycol ether
• active compound 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
• Seeds of the test plants are sown in normal soil. After 24 hours, the soil is watered with the preparation of the active compound. In this context, it is expedient to keep the amount of water per unit area constant. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
• the figures denote:

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Dentistry (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Agronomy & Crop Science (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Plural Heterocyclic Compounds (AREA)

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• 1994
  • 1994-05-02 DE DE4415338A patent/DE4415338A1/de not_active Withdrawn
• 1995
  • 1995-04-19 EP EP95917938A patent/EP0758326B1/de not_active Expired - Lifetime
  • 1995-04-19 CN CN95193810A patent/CN1073561C/zh not_active Expired - Fee Related
  • 1995-04-19 WO PCT/EP1995/001472 patent/WO1995029905A1/de active IP Right Grant
  • 1995-04-19 JP JP7527963A patent/JPH09512281A/ja active Pending
  • 1995-04-19 KR KR1019960706128A patent/KR100369704B1/ko not_active IP Right Cessation
  • 1995-04-19 AU AU24069/95A patent/AU2406995A/en not_active Abandoned
  • 1995-04-19 US US08/732,239 patent/US5827800A/en not_active Expired - Fee Related
  • 1995-04-19 DE DE59509781T patent/DE59509781D1/de not_active Expired - Fee Related

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